Dye transfer inhibiting compositions comprising bleaching agents and a polyamine N-oxide polymer

ABSTRACT

The present invention relates to dye transfer inhibiting compositions comprising: a) a polymer selected from polyamine N-oxide containing polymers which contain a polymersiable unit, whereto the N-O group can be attached to or wherein the N-O group forms part of the polymersiable unit or a combination of both; and a moiety which can be an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or allcyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group form part of these groups; a preferred polymer is poly(4-vinylpyridine-N-oxide); and b) a bleaching agent.

FIELD OF THE INVENTION

The present invention relates to a composition and a process forinhibiting dye transfer between fabrics during washing. More inparticular, this invention relates to dye transfer inhibitingcompositions comprising polyamine N-oxide containing polymers andbleaching agents.

BACKGROUND OF THE INVENTION

Bleaching agents have been commonly used in detergent compositions toassist in stain removal, as well as for whitening of fabrics.

In general, bleaches remove soil and colored stains from fabrics byoxidation to make the soil or stain more soluble, and thus more easilyto remove it. Bleaches have also been used to whiten light coloredfabrics that have suffered from yellowing over time and use.

The relative ability of the bleaching agent to meet various performancecriteria is among others depending on the presence of adjunct detergentingredients. As a consequence, the detergent formulator is faced with adifficult task of providing detergent compositions which have anexcellent overall performance.

One of the types of adjunct detergent ingredients that is added todetergent compositions are dye transfer inhibiting polymers.

Said polymers are added to detergent compositions in order to inhibitthe transfer of dyes from colored fabrics onto other fabrics washedtherewith. These polymers have the ability to complex or adsorb thefugitive dyes washed out of dyed fabrics before the dyes have theopportunity to become attached to other articles in the wash.

Polymers have been used within detergent compositions to inhibit dyetransfer. Copending European Patent Application N° 92202168.8 describespolyamine N-oxide containing polymers which are very efficient ineliminating transfer of solubilized or suspended dyes.

It has now been found that polyamine N-oxide containing polymers arevery compatible with bleaching agents. In addition, it has been foundthat the dye transfer inhibiting performance of the polyamine N-oxidecontaining polymers has been increased in the presence of bleachingagents.

This finding allows us to formulate detergent compositions which haveboth excellent dye transfer inhibiting properties and overall detergencyperformance.

According to another embodiment of this invention a process is alsoprovided for laundering operations involving colored fabrics.

SUMMARY OF THE INVENTION

The present invention relates to inhibiting dye transfer compositionscomprising

a) a polymer selected from polyamine N-oxide containing polymers whichcontain units having the following structure formula (I): ##STR1##wherein P is a polymerisable unit, whereto the N-O group can be attachedto or wherein the N-O group forms part of the polymerisable unit or acombination of both. ##STR2## R are aliphatic, ethoxylated aliphatics,aromatic, heterocyclic or alicyclic groups or any combination thereofwhereto the nitrogen of the N-O group can be attached or wherein thenitrogen of the N-O group form part of these groups.

b) a bleaching agent

DETAILED DESCRIPTION OF THE INVENTION

The compositions of the present invention comprise as an essentialelement polyamine N-oxide containing polymers which contain units havingthe following structure formula: ##STR3## wherein P is a polymerisableunit, whereto the R-N-O group can be attached to or wherein the R-N-Ogroup forms part of the polymerisable unit or a combination of both.##STR4## R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclicor alicyclic groups or any combination thereof whereto the nitrogen ofthe N-O group can be attached or wherein the nitrogen of the N-O groupis part of these groups.

The N-O group can be represented by the following general structures:##STR5## wherein R1, R2, R3 are aliphatic groups, aromatic, heterocyclicor alicyclic groups or combinations thereof, x or/and y or/and z is 0 or1 and wherein the nitrogen of the N-O group can be attached or whereinthe nitrogen of the N-O group forms part of these groups.

The N-O group can be part of the polymerisable unit (P) or can beattached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of thepolymerisable unit comprise polyamine N-oxides wherein R is selectedfrom aliphatic, aromatic, alicyclic or heterocyclic groups.

One class of said polyamine N-oxides comprises the group of polyamineN-oxides wherein the nitrogen of the N-O group forms part of theR-group. Preferred polyamine N-oxides are those wherein R is aheterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine,piperidine, quinoline, acridine and derivatives thereof.

Another class of said polyamine N-oxides comprises the group ofpolyamine N-oxides wherein the nitrogen of the N-O group is attached tothe R-group.

Other suitable polyamine N-oxides are the polyamine oxides whereto theN-O group is attached to the polymerisable unit. Preferred class ofthese polyamine N-oxides are the polyamine N-oxides having the generalformula (I) wherein R is an aromatic, heterocyclic or alicyclic groupswherein the nitrogen of the N-O functional group is part of said Rgroup.

Examples of these classes are polyamine oxides wherein R is aheterocyclic compound such as pyridine, pyrrole, imidazole andderivatives thereof.

Another preferred class of polyamine N-oxides are the polyamine oxideshaving the general formula (I) wherein R are aromatic, heterocyclic oralicyclic groups wherein the nitrogen of the N-O functional group isattached to said R groups. Examples of these classes are polyamineoxides wherein R groups can be aromatic such as phenyl.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof.

The amine N-oxide polymers of the present invention typically have aratio of amine to the amine N-oxide of 10:1 to 1:1000000. However theamount of amine oxide groups present in the polyamine N-oxide containingpolymer can be varied by appropriate copolymerization or by appropriatedegree of N-oxidation. Preferably, the ratio of amine to amine N-oxideis from 2:3 to l:1000000. More preferably from 1:4 to 1:1000000, mostpreferably from 1:7 to 1:1000000. The polymers of the present inventionactually encompass random or block copolymers where one monomer type isan amine N-oxide and the other monomer type is either an amine N-oxideor not. The amine oxide unit of the polyamine N-oxides has a PKa<10,preferably PKa<7, more preferred PKa<6.

The polyamine N-oxide containing polymer can be obtained in almost anydegree of polymerisation. The degree of polymerisation is not criticalprovided the material has the desired water-solubility anddye-suspending power. Typically, the average molecular weight of thepolyamine N-oxide containing polymer is within the range of 500 to1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to30,000, most preferably from 3,000 to 20,000.

The polyamine N-oxide containing polymers of the present invention aretypically present from 0,001% to 10%, more preferably from 0.01% to 2%,most preferred from 0.05% to 1% by weight of the dye transfer inhibitingcomposition. The present compositions are conveniently used as additivesto conventional detergent compositions for use in laundry operations.The present invention also encompasses dye transfer inhibitingcompositions which will contain detergent ingredients and thus serve asdetergent compositions.

Methods for making polyamine N-oxides:

The production of the polyamine-N-oxide containing polymers may beaccomplished by polymerizing the amine monomer and oxidizing theresultant polymer with a suitable oxidizing agent, or the amine oxidemonomer may itself be polymerized to obtain the polyamine N-oxide.

The synthesis of polyamine N-oxide containing polymers can beexemplified by the synthesis of polyvinyl-pyridine N-oxide.Poly-4-vinylpyridine ex Polysciences (mw. 50 000, 5.0 g., 0.0475 mole)was predisolved in 50 ml acetic acid and treated with a peracetic acidsolution (25 g of glacial acetic acid, 6.4 g of a 30% vol. solution ofH₂ O₂, and a few drops of H₂ SO₄ give 0.0523 mols of peracetic acid) viaa pipette. The mixture was stirred over 30 minutes at ambienttemperature (32° C.). The mixture was then heated to 80°-85° C. using anoil bath for 3 hours before allowing to stand overnight. The polymersolution then obtained is mixed with 11 of acetone under agitation. Theresulting yellow brown viscous syrup formed on the bottom is washedagain with 11 of acetone to yield a pale crystalline solid.

The solid was filtered off by gravity, washed with acetone and thendried over P₂ O₅.

The amine: amine N-oxide ratio of this polymer is 1:4 (determined byNMR).

BLEACHING AGENT

The detergent compositions hereof contain oxygen bleaching agentcomponents. These bleaching agent components can include one or moreoxygen bleaching agents and, depending upon the bleaching agent chosen,one or more bleach activators. When present bleaching compounds willtypically be present at levels of from about 1% to about 10%, of thedetergent composition. In general, bleaching compounds are optionalcomponents in nonliquid formulations, e.g. granular detergents. Ifpresent, the amount of bleach activators will typically be from about0.1% to about 60%, more typically from about 0.5% to about 40% of thebleaching composition.

The bleaching agent component for use herein can be any of the bleachingagents useful for detergent compositions including oxygen bleaches aswell as others known in the art.

In a method aspect, this invention further provides a method forcleaning fabrics, fibers, textiles, at temperatures below about 50° C.,especially below about 40° C., with a detergent composition containingpolyamine N-oxide containing polymers, optional auxiliary detersivesurfactants, optional detersive adjunct ingredients, and a bleachingagent. The bleaching agent suitable for the present invention can be anactivated or non-activated bleaching agent.

One category of oxygen bleaching agent that can be used encompassespercarboxylic acid bleaching agents and salts thereof. Suitable examplesof this class of agents include magnesium monoperoxyphthalatehexahydrate, the magnesium salt of meta-chloro perbenzoic acid,4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, U.S.patent application Ser. No. 740,446, European Patent Application0,133,354 and U.S. Pat. No. 4,412,934. Highly preferred bleaching agentsalso include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.Pat. No. 4,634,551.

Another category of bleaching agents that can be used encompasses thehalogen bleaching agents. Examples of hypohalite bleaching agents, forexample, include trichloro isocyanuric acid and the sodium and potassiumdichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides.Such materials are normally added at 0.5-10% by weight of the finishedproduct, preferably 1-5% by weight.

Preferably, the bleaches suitable for the present invention includeperoxygen bleaches. Examples of suitable water-soluble solid peroxygenbleaches include hydrogen peroxide releasing agents such as hydrogenperoxide, perborates, e.g. perborate monohydrate, perboratetetrahydrate, persulfates, percarbonates, peroxydisulfates,perphosphates and peroxyhydrates. Preferred bleaches are percarbonatesand perborates.

The hydrogen peroxide releasing agents can be used in combination withbleach activators such as tetraacetylethylenediamine (TAED),nonanoyloxybenzenesulfonate (NOBS, described U.S. Pat. No. 4,412,934),3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to form aperacid as the active bleaching species, leading to improved bleachingeffect. Also suitable activators are acylated citrate esters (ATC) suchas disclosed in Copending European Patent Application No. 91870207.7.

The hydrogen peroxide may also be present by adding an enzymatic system(i.e. an enzyme and a substrate therefore) which is capable ofgenerating hydrogen peroxide at the beginning or during the washingand/or rinsing process. Such enzymatic systems are disclosed in EPPatent Application 91202655.6 filed Oct. 9, 1991.

Other peroxygen bleaches suitable for the present invention includeorganic peroxyacids such as percarboxylic acids.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. Thesematerials can be deposited upon the substrate during the washingprocess. Upon irradiation with light, in the presence of oxygen, such asby hanging clothes out to dry in the daylight, the sulfonated zincphthalocyanine is activated and, consequently, the substrate isbleached. Preferred zinc phthalocyanine and a photoactivated bleachingprocess are described in U.S. Pat. No. 4,033,718. Typically, detergentcompositions will contain about 0.025% to about 1.25%, by weight, ofsulfonated zinc phthalocyanine.

DETERGENT ADJUNCTS

A wide range of surfactants can be used in the detergent compositions. Atypical listing of anionic, nonionic, ampholytic and zwitterionicclasses, and species of these surfactants, is given in U.S. Pat. No.3,664,961 issued to Norris on May 23, 1972.

Mixtures of anionic surfactants are particularly suitable herein,especially mixtures of sulphonate and sulphate surfactants in a weightratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferablyfrom 3:1 to 1:1. Preferred sulphonates include alkyl benzene sulphonateshaving from 9 to 15, especially 11 to 13 carbon atoms in the alkylradical, and alpha-sulphonated methyl fatty acid esters in which thefatty acid is derived from a C₁₂ -C₁₈ fatty source preferably from a C₁₆-C₁₈ fatty source. In each instance the cation is an alkali metal,preferably sodium. Preferred sulphate surfactants are alkyl sulphateshaving from 12 to 18 carbon atoms in the alkyl radical, optionally inadmixture with ethoxy sulphates having from 10 to 20, preferably 10 to16 carbon atoms in the alkyl radical and an average degree ofethoxylation of 1 to 6. Examples of preferred alkyl sulphates herein aretallow alkyl sulphate, coconut alkyl sulphate, and C₁₄₋₁₅ alkylsulphates. The cation in each instance is again an alkali metal cation,preferably sodium.

One class of nonionic surfactants useful in the present invention arecondensates of ethylene oxide with a hydrophobic moiety to provide asurfactant having an average hydrophiliclipophilic balance (HLB) in therange from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic oraromatic in nature and the length of the polyoxyethylene group which iscondensed with any particular hydrophobic group can be readily adjustedto yield a water-soluble compound having the desired degree of balancebetween hydrophilic and hydrophobic elements.

Especially preferred nonionic surfactants of this type are the C₉ -C₁₅primary alcohol ethoxylates containing 3-8 moles of ethylene oxide permole of alcohol, particularly the C₁₄ -C₁₅ primary alcohols containing6-8 moles of ethylene oxide per mole of alcohol and the C₁₂ -C₁₄ primaryalcohols containing 3-5 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfactants comprises alkyl polyglucosidecompounds of general formula

    RO(C.sub.n H.sub.2n O).sub.t Z.sub.x

wherein Z is a moiety derived from glucose; R is a saturated hydrophobicalkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10and n is 2 or 3; x is from 1.3 to 4, the compounds including less than10% unreacted fatty alcohol and less than 50% short chain alkylpolyglucosides. Compounds of this type and their use in detergent aredisclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.

Also suitable as nonionic surfactants are poly hydroxy fatty acid amidesurfactants of the formula ##STR6## wherein R¹ is H, or R¹ is C₁₋₄hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R²is C₅₋₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linearhydrocarbyl chain with at least 3 hydroxyls directly connected to thechain, or an alkoxylated derivative thereof. Preferably, R¹ is methyl,R² is a straight C₁₁₋₁₅ alkyl or alkenyl chain such as coconut alkyl ormixtures thereof, and Z is derived from a reducing sugar such asglucose, fructose, maltose, lactose, in a reductive amination reaction.

The compositions according to the present invention may further comprisea builder system. Any conventional builder system is suitable for useherein including aluminosilicate materials, silicates, polycarboxylatesand fatty acids, materials such as ethylenediamine tetraacetate, metalion sequestrants such as aminopolyphosphonates, particularlyethylenediamine tetramethylene phosphonic acid and diethylene triaminepentamethylenephosphonic acid. Though less preferred for obviousenvironmental reasons, phosphate builders can also be used herein.

Suitable builders can be an inorganic ion exchange material, commonly aninorganic hydrated aluminosilicate material, more particularly ahydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.

Another suitable inorganic builder material is layered silicate, e.g.SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting ofsodium silicate (Na₂ Si₂ O₅).

Suitable polycarboxylates containing one carboxy group include lacticacid, glycolic acid and ether derivatives thereof as disclosed inBelgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylatescontaining two carboxy groups include the water-soluble salts ofsuccinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid,diglycollic acid, tartaric acid, tartronic acid and fumaric acid, aswell as the ether carboxylates described in German Offenlegenschrift2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinylcarboxylates described in Belgian Patent No. 840,623. Polycarboxylatescontaining three carboxy groups include, in particular, water-solublecitrates, aconitrates and citraconates as well as succinate derivativessuch as the carboxymethyloxysuccinates described in British Patent No.1,379,241, lactoxysuccinates described in Netherlands Application7205873, and the oxypolycarboxylate materials such as2-oxa-1,1,3-propane tricarboxylates described in British Patent No.1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxy 1 ares and1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfosubstituents include the sulfosuccinate derivatives disclosed in BritishPatent Nos. 1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, andthe sulfonated pyrolysed citrates described in British Patent No.1,082,179, while polycarboxylates containing phosphone substituents aredisclosed in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates includecyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienidepentacarboxylates, 2,3,4,5-tetrahydrofuran--cis, cis,cis-tetracarboxylates, 2,5-tetrahydrofuran --cis-dicarboxylates,2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane--hexacarboxylates and and carboxymethyl derivatives of polyhydricalcohols such as sorbitol, mannitol and xylitol. Aromaticpolycarboxylates include mellitic acid, pyromellitic acid and thephtalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylatescontaining up to three carboxy groups per molecule, more particularlycitrates. Preferred builder systems for use in the present compositionsinclude a mixture of a water-insoluble aluminosilicate builder such aszeolite A or of a layered silicate (sks/6), and a water-solublecarboxylate chelating agent such as citric acid.

A suitable chelant for inclusion in the detergent compositions inaccordance with the invention is ethylenediamine-N,N'-disuccinic acid(EDDS) or the alkali metal, alkaline earth metal, ammonium, orsubstituted ammonium salts thereof, or mixtures thereof. Preferred EDDScompounds are the free acid form and the sodium or magnesium saltthereof. Examples of such preferred sodium salts of EDDS include Na₂EDDS and Na₄ EDDS. Examples of such preferred magnesium salts of EDDSinclude MgEDDS and Mg₂ EDDS. The magnesium salts are the most preferredfor inclusion in compositions in accordance with the invention.

Especially for the liquid execution herein, suitable fatty acid buildersfor use herein are saturated or unsaturated C10-18 fatty acids, as wellas the corresponding soaps. Preferred saturated species have from 12 to16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acidis oleic acid. Preferred builder systems for use in granularcompositions include a mixture of a water-insoluble aluminosilicatebuilder such as zeolite A, and a watersoluble carboxylate chelatingagent such as citric acid. Other builder materials that can form part ofthe builder system for use in granular compositions include inorganicmaterials such as alkali metal carbonates, bicarbonates, silicates, andorganic materials such as the organic phosphonates, amiono polyalkylenephosphonates and amino polycarboxylates.

Other suitable water-soluble organic salts are the homo- or co-polymericacids or their salts, in which the polycarboxylic acid comprises atleast two carboxyl radicals separated from each other by not more thantwo carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756.Examples of such salts are polyacrylates of MW 2000-5000 and theircopolymers with maleic anhydride, such copolymers having a molecularweight of from 20,000 to 70,000, especially about 40,000.

Detergency builder salts are normally included in amounts of from 10% to80% by weight of the composition preferably from 20% to 70% and mostusually from 30% to 60% by weight.

Other detergent ingredients that can be included are detersive enzymeswhich can be included in the detergent formulations for a wide varietyof purposes including removal of protein-based, carbohydrate-based, ortriglyceride-based stains, for example, and prevention of refugee dyetransfer. The enzymes to be incorporated include proteases, amylases,lipases, cellulases, and peroxidases, as well as mixtures thereof. Othertypes of enzymes may also be included. They may be of any suitableorigin, such as vegetable, animal, bacterial, fungal and yeast origin.

Enzymes are normally incorporated at levels sufficient to provide up toabout 5 mg by weight, more typically about 0.05 mg to about 3 mg, ofactive enzyme per gram of the composition.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B.licheniforms. Proteolyticenzymes suitable for removing protein-based stains that are commerciallyavailable include those sold under the tradenames Alcalase, Savinase andEsperase by Novo Industries A/S (Denmark) and Maxatase by InternationalBio-Syntnetics, Inc. (The Netherlands) and FN-base by Genencor, Optimaseand opticlean by MKC.

Of interest in the category of proteolytic enzymes, especially forliquid detergent compositions, are enzymes referred to herein asProtease A and Protease B. Protease A is described in European PatentApplication 130,756. Protease B is described in European PatentApplication Serial No. 87303761.8.

Amylases include, for example, -amylases obtained from a special strainof B. licheniforms, described in more detail in British PatentSpecification No. 1,296,839 (Novo). Amylolytic proteins include, forexample, Rapidase, Maxamyl (International Bio-Synthetics, Inc.) andTermamyl, (Novo Industries).

The cellulases usable in the present invention include both bacterial orfungal cellulase. Preferably, they will have a pH optimum of between 5and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,Barbesgoard et al, which discloses fungal cellulase produced fromHumicola insolens. Suitable cellulases are also disclosed inGB-A-2,075.028 ; GB-A-2.095,275 and DE-OS-2,247,832.

Examples of such cellulases are cellulases produced by a strain ofHumicola insolens (Humicola grisea var. thermoidea), particularly theHumicola strain DSM 1800, and cellulases produced by a fungus ofBacillus N or a cellulase 212-producing fungus belonging to the genusAeromonas, and cellulase extracted from the hepatopancreas of a marinemollusc (Dolabella Auricula Solander).

Other suitable cellulases are cellulases originated from HumicolaInsulens having a molecular weight of about 50 KDa, an isoelectric pointof 5.5 and containing 415 amino acids. Such cellulase are described inCopending European patent application No. 93200811.3, filed Mar. 19,1993. Especially suitable cellulase are the cellulase having color carebenefits. Examples of such cellulases are cellulase described inEuropean patent application No. 91202879.2, filed November 6, 1991Carezyme (Novo).

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipasesinclude those which show a positive immunoligical cross-reaction withthe antibody of the lipase, produced by the microorganism Pseudomonasfluorescent IAM 1057. This lipase is available from Amano PharmaceuticalCo. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,"hereinafter referred to as "Amano-P". Especially suitable Lipase arelipase such as M1 Lipase (Ibis) and Lipolase (Novo).

Peroxidase enzymes are used in combination with oxygen sources, e.g.percarbonate, perborate, persulfate, hydrogen peroxide, etc. They areused for "solution bleaching" i.e. to prevent transfer of dyes ofpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT Internation Application WO 89/099813 and in European Patentapplication EP No. 91202882.6, filed on Nov. 6, 1991.

In liquid formulations, an enzyme stabilization system is preferablyutilized. Enzyme stabilization techniques for aqueous detergentcompositions are well known in the art. For example, one technique forenzyme stabilization in aqueous solutions involves the use of freecalcium ions from sources such as calcium acetate, calcium formate andcalcium propionate. Calcium ions can be used in combination with shortchain carboxylic acid salts, preferably formates. See, for example, U.S.Pat. No. 4,318,818. It has also been proposed to use polyols likeglycerol and sorbitol. Alkoxy-alcohols, dialkylglycoethers, mixtures ofpolyvalent alcohols with polyfunctional aliphatic amines (e.g., such asdiethanolamine, triethanolamine, di-isopropanolamime, etc.), and boricacid or alkali metal borate. Enzyme stabilization techniques areadditionally disclosed and exemplified in U.S. Pat. 4,261,868, U.S. Pat.No. 3,600,319, and European Patent Application Publication No. 0 199405, Application No. 86200586.5. Non-boric acid and borate stabilizersare preferred. Enzyme stabilization systems are also described, forexample, in U.S. Pat. Nos. 4,261,868, 3,600,319 and 3,519,570.

Other suitable detergent ingredients that can be added are enzymeoxidation scavengers which are described in Copending European Patentaplication N 92870018.6 filed on Jan. 31, 1992. Examples of such enzymeoxidation scavengers are ethoxylated tetraethylene polyamines.Especially preferred detergent ingredients are combinations withtechnologies which also provide a type of color care benefit. Examplesof these technologies are polyvinylpyrrolidone polymers and otherpolymers which have dye transfer inhibiting properties. Other examplesare cellulase and/or peroxidases and/or metallo catalysts for colormainrance rejuvenation. Such metallo catalysts are described incopending European Patent Application No. 92870181.2. In addition, ithas been found that the polyamine-N-oxide containing polymers eliminateor reduce the deposition of the metallo-catalyst onto the fabricsresulting in improved whiteness benefit.

Another optional ingredient is a suds suppressor, exemplified bysilicones, and silica-silicone mixtures. Silicones can be generallyrepresented by alkylated polysiloxane materials while silica is normallyused in finely divided forms exemplified by silica aerogels and xerogelsand hydrophobic silicas of various types. These materials can beincorporated as particulates in which the suds suppressor isadvantageously releasably incorporated in a water-soluble orwater-dispersible, substantially non-surface-active detergentimpermeable carrier. Alternatively the suds suppressor can be dissolvedor dispersed in a liquid carrier and applied by spraying on to one ormore of the other components.

A preferred silicone suds controlling agent is disclosed in Bartollotaet al. U.S. Pat. No. 3 933 672. Other particularly useful sudssuppressors are the self-emulsifying silicone suds suppressors,described in German Patent Application DTOS 2 646 126 published Apr. 28,1977. An example of such a compound is DC-544, commercially availablefrom Dow Corning, which is a siloxane-glycol copolymer. Especiallypreferred suds controlling agent are the suds suppressor systemcomprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable2-alkyl-alcanols are 2-butyl-octanol which are commercially availableunder the trade name Isofol 12 R. Such suds suppressor system aredescribed in Copending European Patent application N 92870174.7 filed 10Nov., 1992.

Especially preferred silicone suds controlling agents are described inCopending European Patent application N° 92201649.8 Said compositionscan comprise a silicone/silica mixture in combination with fumednonporous silica such as Aerosil^(R).

The suds suppressors described above are normally employed at levels offrom 0.001% to 2% by weight of the composition, preferably from 0.01% to1% by weight.

Other components used in detergent compositions may be employed, such assoil-suspending agents soil-release agents, optical brighteners,abrasives, bactericides, tarnish inhibitors, coloring agents, and/orencapsulated or more encapsulated perfumes.

Antiredeposition and soil suspension agents suitable herein includecellulose derivatives such as methylcellulose, carboxymethylcelluloseand hydroxyethylcellulose, and homo- or co-polymeric polycarboxylicacids or their salts. Polymers of this type include the polyacrylatesand maleic anhydride-acrylic acid copolymers previously mentioned asbuilders, as well as copolymers of maleic anhydride with ethylene,methylvinyl ether or methacrylic acid, the maleic anhydride constitutingat least 20 mole percent of the copolymer. These materials are normallyused at levels of from 0.5% to 10% by weight, more preferably from 0.75%to 8%, most preferably from 1% to 6% by weight of the composition.

Preferred optical brighteners are anionic in character, examples ofwhich are disodium 4,4¹ -bis-(2-diethanolamino-4-anilino --s--triazin-6-ylamino)stilbene-2:2¹ disulphonate, disodium 4, --4¹-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2¹--disulphonate, disodium 4,4¹--bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2¹ --disulpnonate,monosodium 4¹,4¹¹-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2-sulphonate, disodium4,4¹-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2¹-disulphonate, disodium 4,4¹-bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2¹ disulphonate, disodium4,4¹bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2¹disulphonate and sodium 2(stilbyl-4¹¹ -(naphtho-1¹,2¹:4,5)-1,2,3-triazole-2¹¹ -sulphonate.

Other useful polymeric materials are the polyethylene glycols,particularly those of molecular weight 1000-10000, more particularly2000 to 8000 and most preferably about 4000. These are used at levels offrom 0.20% to 5% more preferably from 0.25% to 2.5% by weight. Thesepolymers and the previously mentioned homo- or co-polymericpolycarboxylate salts are valuable for improving whiteness maintenance,fabric ash deposition, and cleaning performance on clay, proteinaceousand oxidizable soils in the presence of transition metal impurities.

Soil release agents useful in compositions of the present invention areconventionally copolymers or terpolymers of terephthalic acid withethylene glycol and/or propylene glycol units in various arrangements.Examples of such polymers are disclosed in the commonly assigned U.S.Pat. Nos. 4,116,885 and 4,711,730 and European Published PatentApplication No. 0 272 033. A particular preferred polymer in accordancewith EP-A-0 272 033 has the formula

    (CH.sub.3 (PEG).sub.43).sub.0.75 (POH).sub.0.25 [T-PO).sub.2.8 (T-PEG).sub.0.4 ]T(POH).sub.0.25 ((PEG).sub.43 CH.sub.3).sub.0.75

where PEG is --(OC₂ H₄)O--, PO is (OC₃ H₆ O) and T is (pcOC₆ H₄ CO).

Also very useful are modified polyesters as random copolymers ofdimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and1-2 propane diol, the end groups consisting primarily of sulphobenzoateand secondarily of mono esters of ethylene glycol and/or propane-diol.The target is to obtain a polymer capped at both end by sulphobenzoategroups, "primarily", in the present context most of said copolymersherein will be end-capped by sulphobenzoate groups. However, somecopolymers will be less than fully capped, and therefore their endgroups may consist of monoester of ethylene glycol and/or propane 1-2diol, thereof consist "secondarily" of such species.

The selected polyesters herein contain about 46% by weight of dimethylterephtalic acid, about 16% by weight of propane -1.2 diol, about 10% byweight ethylene glycol about 13% by weight of dimethyl sulfobenzoid acidand about 15% by weight of sulfoisophtalic acid, and have a molecularweight of about 3.000. The polyesters and their method of preparationare described in detail in EPA 311 342.

The detergent compositions according to the invention can be in liquid,paste, gels or granular forms. Granular compositions according to thepresent invention can also be in "compact form", i.e. they may have arelatively higher density than conventional granular detergents, i.e.from 550 to 950 g/l; in such case, the granular detergent compositionsaccording to the present invention will contain a lower amount of"inorganic filler salt", compared to conventional granular detergents;typical filler salts are alkaline earth metal salts of sulphates andchlorides, typically sodium sulphate; "compact" detergents typicallycomprise not more than 10% filler salt. The liquid compositionsaccording to the present invention can also be in "concentrated form",in such case, the liquid detergent compositions according to the presentinvention will contain a lower amount of water, compared to conventionalliquid detergents. Typically, the water content of the concentratedliquid detergent is less than 30%, more preferably less than 20%, mostpreferably less than 10% by weight of the detergent compositions. Otherexamples of liquid compositions are anhydrous compositions containingsubstantially no water. Both aqueous and non-aqueous liquid compositionscan be structured or non-structured.

The present invention also relates to a process for inhibiting dyetransfer from one fabric to another of solubilized and suspended dyesencountered during fabric laundering operations involving coloredfabrics.

The process comprises contacting fabrics with a laundering solution ashereinbefore described.

The process of the invention is conveniently carried out in the courseof the washing process. The washing process is preferably carried out at5° C. to 75° C., especially 20° to 60°, but the polymers are effectiveat up to 95° C. and higher temperatures. The pH of the treatmentsolution is preferably from 7 to 11, especially from 7.5 to 10.5.

The process and compositions of the invention can also be used asdetergent additive products. Such additive products are intended tosupplement or boost the performance of conventional detergentcompositions. The detergent compositions according to the presentinvention include compositions which are to be used for cleaningsubstrates, such as fabrics, fibers, hard surfaces, skin etc., forexample hard surface cleaning compositions (with or without abrasives),laundry detergent compositions, automatic and non automatic dishwashingcompositions.

The following examples are meant to exemplify compositions of thepresent invention, but are not necessarily meant to limit or otherwisedefine the scope of the invention, said scope being determined accordingto claims which follow.

A granular detergent composition according to the present invention isprepared, having the following compositions:

                  TABLE I                                                         ______________________________________                                        % by weight of the total detergent composition                                Linear alkyl benzene sulphonate                                                                      11.40                                                  Tallow alkyl sulphate  1.80                                                   C.sub.45  alkyl sulphate                                                                             3.00                                                   C.sub.45  alcohol 7 times ethoxylated                                                                4.00                                                   Tallow alcohol 11 times ethoxylated                                                                  1.80                                                   Dispersant             0.07                                                   Silicone fluid         0.80                                                   Trisodium citrate      14.00                                                  Citric acid            3.00                                                   Zeolite                32.50                                                  Maleic acid actylic acid copolymer                                                                   5.00                                                   Cellulase (active protein)                                                                           0.03                                                   Lipase                 0.36                                                   Sodium silicate        2.00                                                   Sodium sulphate        3.50                                                   ______________________________________                                    

EXAMPLE I

The extent of dye transfer from different colored fabrics was studiedusing a launder-o-meter test that simulates a 30 min wash cycle. Thelaunder-o-meter beaker contains 200 ml of a detergent solution, a 10cm×10 cm piece of the colored fabric and a multifiber swatch which isused as a pick-up tracer for the bleeding dye. The multifiber swatchconsists of 6 pieces (1.5 cm×5 cm each) of different material(polyacetate, cotton, polyamide, polyester, wool and orlon) which aresewn together.

The extent of dye transfer is assessed by a Hunter Colour measurement.The Hunter Colour system evaluates the colour of a fabric sample interms of the ΔE value which represents the change in the Hunter L, a, b,values which are determined by reflecting spectrophctometer. The ΔEvalue is defined by the following equation:

    ΔE={(a.sub.f -a.sub.i).sup.2 +(b.sub.f -b.sub.i).sup.2 +(L.sub.f -L.sub.i).sup.2 }.sup.1/2

where the subscripts i and f refer to the Hunter value before and afterwashing in the presence of the bleeding fabric, respectively. The leastsignificant difference is 1 at 95% confidence level.

Example I demonstrates the increased dye transfer inhibiting performanceof the polyamine N-oxide containing polymers in combination withbleaching agents. The bleaching agent that is used is an activatedbleaching agent (Perborate (PB)/TAED). The performance of saidcombination was determined by measuring the whiteness of textile itemswashed with compositions containing the PB/TAED and/or poly (4-vinylpyridine-N-oxide) (PVNO).

EXPERIMENTAL CONDITIONS

pH=10

Wash Temperature: 40° C.

A: A detergent composition according to Table I which contains noPB/TAED and no PVNO (poly(4-vinylpyridine-N-oxide).

B: A detergent composition according to Table I which contains 16% PBand 5% TAED and no PVNO (poly(4-vinylpyridine-N-oxide).

C: A detergent composition according to Table I containing 10 ppm ofPVNO (poly(4-vinylpyridine-N-oxide)) which has an average molecularweight of about 30,000 and an amine to amine N-oxide ratio of 1:10(measured by NMR).

D: A detergent composition according to Table I containing 10 ppm ofPVNO (poly(4-vinylpyridine-N-oxide)) which has an average molecularweight of about 30,000 and an amine to amine N-oxide ratio of 1:10(measured by NMR) and 16% PB, 5% TAED.

Results: ΔE values for the cotton pick-up tracer.

    ______________________________________                                        Bleeding fabric                                                                         Bleeding fabric                                                     composition                                                                             color       A      B      C    D                                    ______________________________________                                        100% cotton                                                                             Direct Blue 90                                                                            23.1   21.6   6.9  4.5                                  ______________________________________                                    

EXAMPLE II (A/B/C)

A liquid detergent composition according to the present invention isprepared, having the following compositions:

    ______________________________________                                        % by weight of the total detergent composition                                                    A        B      C                                         ______________________________________                                        Linear alkylbenzene sulfonate                                                                     10       --     --                                        Polyhydroxy fatty acid amide                                                                      --       9      --                                        Alkyl alkoxylated sulfate                                                                         --       --     9                                         Alkyl sulphate      4        4      4                                         Patty alcohol (C.sub.12 -C.sub.15) ethoxylate                                                     12       12     12                                        Fatty acid          10       10     10                                        Oleic acid          4        4      4                                         Citric acid         1        1      1                                         Diethylenetriaminepentamethylene                                                                  1.5      1.5    1.5                                       Phosphonic acid                                                               NaOH                3.4      3.4    3.4                                       Propanediol         1.5      1.5    1.5                                       Ethanol             10       10     10                                        Ethoxylated tetraethylene pentamine                                                               0.7      0.7    0.7                                       Poly(4-vinylpyridine)-N-oxide                                                                     0-1      0-1    0-1                                       Thermamyl           0.13     0.13   0.13                                      Carezyme            0.014    0.014  0.014                                     FN-Base             1.8      1.8    1.8                                       Lipolase            0.14     0.14   0.14                                      Endoglucanase A     0.53     0.53   0.53                                      Suds supressor (ISOFOL.sup.r)                                                                     2.5      2.5    2.5                                       H.sub.2 O.sub.2     7.5      7.5    7.5                                       ATC                 5        5      5                                         Minors              up to 100                                                 ______________________________________                                    

EXAMPLE III (A/B/C)

A compact granular detergent composition according to the presentinvention is prepared, having the following formulation:

    ______________________________________                                        % by vaight of the total detergent composition                                                    A        B      C                                         ______________________________________                                        Linear alkyl benzene sulphonate                                                                   11.40    --     --                                        Polyhydroxy fatty acid amide                                                                      --       10     --                                        Alkyl alkoxylated sulfate                                                                         --       --     9                                         Tallow alkyl sulphate                                                                             1.80     1.80   1.80                                      C.sub.45 alkyl sulphate                                                                           3.00     3.00   3.00                                      C.sub.45 alcohol 7 times ethoxylated                                                              4.00     4.00   4.00                                      Tallow alcohol 11 times ethoxylated                                                               1.80     1.80   1.80                                      Dispersant          0.07     0.07   0.07                                      Silicone fluid      0.80     0.80   0.80                                      Trisodium citrate   14.00    14.00  14.00                                     Citric acid         3.00     3.00   3.00                                      Zeolite             32.50    32.50  32.50                                     Maleic acid acrylic acid copolymer                                                                5.00     5.00   5.00                                      Cellulase (active protein)                                                                        0.03     0.03   0.03                                      Alkalase/BAN        0.60     0.60   0.60                                      Lipase              0.36     0.36   0.36                                      Sodium silicate     2.00     2.00   2.00                                      Sodium sulphate     3.50     3.50   3.50                                      Poly(4-vinylpyridine)-N-oxide                                                                     0-1      0-1    0-1                                       Perborate           15       15     15                                        TAED                5        --     5                                         ATC                 --       5      --                                        Minors              up to 100                                                 ______________________________________                                    

The above compositions (Example II (A/B/C) and III (A/B/C)) were verygood at displaying excellent cleaning and detergency performance withoutstanding color-care performance on colored fabrics and mixed loads ofcolored and white fabrics.

We claim:
 1. A dye transfer inhibiting composition for use in aqueouswash solutions comprisinga) a dye transfer inhibiting amount ofpoly(4-vinylpyridine-N-oxide) having a ratio of amine to amine N-oxideof from about 2:3 to about 1:1,000,000; and b) a cleaning effectiveamount of a bleaching agent selected from percarboxylic acids, halogenbleaching agents, perborates, persulfates, percarbonates,peroxydisulfates, perphosphates, peroxyhydrates, bleach activators,hydrogen peroxide-generating enzymes, non-oxygen-type bleaching agents,or mixtures thereof.
 2. A dye transfer inhibiting composition accordingto claim 1 wherein the poly(4-vinylpyridine-N-oxide) polymer has anaverage molecular weight within the range of 500 to 1,000,000.
 3. A dyetransfer inhibiting composition according to claim 1 wherein thepoly(4-vinylpyridine-N-oxide) is present at levels from 0.001 to 10% byweight of the composition.
 4. A dye transfer inhibiting compositionsaccording to claim 1 wherein said bleaching agent is a peroxygenbleaching agent selected from, perberates, persulfates, percarbonates,peroxydisulfates, perphosphates, bleach activators, and peroxyhydratesor mixtures thereof.
 5. A dye transfer inhibiting composition accordingto claim 4 wherein bleach activator is selected fromtetraacetylethylenediamine, nonanoyloxybenzenesulfonate,3,5,5-trimethyihexanoyloxybenzenesulfonate, pentaacetylglucose, acylatedcitrate esters, or mixtures thereof.
 6. A dye transfer inhibitingcomposition according to claim 1 further comprising a metallo-catalystas a bleaching aid.
 7. A dye transfer inhibiting composition accordingto claim 1 which is a detergent additive, in the form of a non-dustinggranule or a liquid.
 8. A detergent composition which comprises a dyetransfer inhibiting composition according to claim 1 further comprisingone or more of the following ingredients: surfactants, builders,chelants, suds suppressor, soil release agents, antiredeposition agents,optical brighteners, abrasives, bactericides, tarnish inhibitors,coloring agents, perfumes, or mixtures thereof
 9. A dye transferinhibiting composition for use in aqueous washing solutions comprisinga)a dye transfer inhibiting mount of poly(4-vinylpyridine-N-oxide) havinga ratio of amine to amine N-oxide of from about 2:3 to about1:1,000,000; b) a cleaning effective amount of a bleaching agent; and c)a cleaning effective amount of a detersire surfactant.
 10. A dyetransfer inhibiting composition according to claim 9 wherein thepoly(4-vinylpyridine-N-oxide)polymer has an average molecular weightwithin the range of 500 to 1,000,000.
 11. A dye transfer inhibitingcomposition according to claim 9 wherein thepoly(4-vinylpyridine-N-oxide) is present at levels from 0.001 to 10% byweight of the composition.
 12. A dye transfer inhibiting compositionaccording to claim 9 further comprising a bleach activator.
 13. A dyetransfer inhibiting composition according to claim 12 wherein saidbleach activator is selected from tetraacetylethylenediamine,nonanoyloxybenzenesulfonate, 3,5,5-trimethylhexanoyloxybenzenesulfonate,pentaacetylglucose, acylated citrate esters, or mixture thereof.
 14. Adye transfer inhibiting composition according to claim 13 furthercomprising a metallo-catalyst as a bleaching aid.
 15. A detergentcomposition which comprises a dye transfer inhibiting compositionaccording to claim 4 further comprising one or more of the followingingredients: builders, chelants, suds suppressor, soil release agents,antiredeposifion agents, optical brighteners, abrasives, bactericides,tarnish inhibitors, coloring agents, perfumes, or mixtures thereof.